|Publication number||US7254983 B2|
|Application number||US 09/981,145|
|Publication date||Aug 14, 2007|
|Filing date||Oct 16, 2001|
|Priority date||Oct 16, 2001|
|Also published as||CA2463652A1, CN1589172A, EP1436066A2, EP1436066A4, US7237428, US20030070487, US20040200735, WO2003033113A2, WO2003033113A3|
|Publication number||09981145, 981145, US 7254983 B2, US 7254983B2, US-B2-7254983, US7254983 B2, US7254983B2|
|Inventors||David H. DaCosta, P. Mark Golben, David C. Tragna|
|Original Assignee||Hera Usa Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (41), Non-Patent Citations (3), Referenced by (3), Classifications (24), Legal Events (9)|
|External Links: USPTO, USPTO Assignment, Espacenet|
1. Field of the Invention
This invention relates generally to hydrogen storage devices and more particularly relates to such devices utilizing metal hydrides for storage of high volume of hydrogen at lower pressures.
2. Background Art
With the increasing use of hydrogen gas in industrial and commercial applications, conventional methods of storing hydrogen as a gas under pressure are seen to present undesirable risks. Hydrogen storage as a gas is typically done in large, bulky steel cylinders at very high pressures (e.g., 2,000 psi).
Hydrogen may be stored in liquid form, typically in insulated containers at very low temperatures. Energy must be used to keep the temperature low to prevent the liquid hydrogen from evaporating or boiling off. Hence, cryogenic hydrogen production and storage is highly inefficient because of the extremely cold temperatures at which the storage vessels must be maintained.
More recently, attention has been directed to the storage of hydrogen in metallic compounds, known as hydrides. Metal hydrides can store large amounts of hydrogen at low pressures and in relatively small volumes. Low pressure storage of hydrogen in containers containing hydrides is relatively safe and allows the construction of hydrogen containers having forms significantly different than those storing gaseous hydrogen. Examples of low pressure hydride storage containers can be found in commonly assigned U.S. Pat. Nos. 5,250,368, 5,532,074 and 5,623,987, which are incorporated by reference herein.
Additionally, hydrogen storage containers are sold by the assignee of the invention under the trade name Ergenics ST-Series hydrogen storage units utilizing hydrides manufactured by the assignee hereof, for example, HY-STORŽ 208 hydride alloys. Additional information about these storage units and hydride alloys is available on the website of the assignee of this invention, found at www.ergenics.com. The use of solid hydridable materials to store hydrogen is also disclosed in numerous patents, such as U.S. Pat. Nos. 3,508,514, 3,516,263, 4,036,944, 5,518,528, 5,697,221 and 5,906,792.
Such metal hydride storage units have many uses and applications in a variety of industrial and laboratory applications and environments. The diversity of applications requires a storage system that can provide the user with a reliable source of hydrogen at a variety of capacities. Small storage units are commonly used as hydrogen sources for laboratory experimentation, as in the examples described above. Much larger units are needed to provide the quantity of hydrogen necessary for vehicular transportation systems or in utility applications. Hydrogen storage systems are needed that will allow for quick and easy use of the hydrogen gas, and the storage system, regardless of the size and capacity of the container, must be robust enough to perform properly and reliably under a wide range of environmental conditions.
Another major consideration is the ability of a user of a hydrogen storage device to measure or gauge the amount of hydrogen gas in the hydride container available for further utilization, as and when needed. An accurate gauge is ideal, but even a gauge of the amount of hydrogen gas availability is desirable that is accurate to within 15-30%.
The construction and normal operation of known metal hydride hydrogen storage systems make it especially difficult to accurately gauge the amount of hydrogen gas available. It is possible to accurately estimate the amount of hydrogen gas available in the above described gas containers which store hydrogen in a gas state from the ideal gas law (PV=nRT), because the amount of hydrogen is directly proportional to the pressure, when temperature is maintained at a constant value. This is possible because in those types of storage systems, the volume, V, and temperature, T, remain essentially constant as an amount of hydrogen gas (n) is utilized and being withdrawn from the system. The utilization of hydrogen gas, as it is withdrawn from the container is indicated by a reduction in the amount of hydrogen (n), and produces a directly proportional reduction in pressure, P. Thus, it is possible to estimate to a very accurate degree, the amount of hydrogen gas available in the container by an accurate reading of the pressure, P.
However, because the hydrogen gas is incorporated into the lattice structure of the metal hydride, storage containers using hydrides cannot rely on the pressure P as a directly proportional measure of the amount of hydrogen gas (n) remaining in the container. It is thus necessary to provide a fairly accurate measure of hydrogen gas contained within a container, similar to a fuel gauge in a standard internal combustion automobile.
Accordingly what is described and claimed as Applicants' invention is a hydrogen gas storage container having a canister with at least one outlet opening for charging and discharging gas, the canister enclosing a metal hydride capable of absorbing and desorbing hydrogen gas and a gauge for measuring the capacity of hydrogen remaining within the hydride material. To further permit distribution of the hydrogen throughout the hydride, a porous matrix may be disposed within said metal hydride material for providing efficient distribution of hydrogen gas to said metal hydride material. The fuel gauge may further comprise subassemblies for determining the hydrogen capacity, and may depend on different principles, for example, a pressure gauge sensitive to the plateau pressure indicative of the hydrogen capacity, a piezoelectric sensor that in combination with a rigid chamber in which hydride material is closely packed provides a pressure differential indicative of hydrogen capacity, or a resistivity sensor that in combination with a chamber in which hydride material is packed provides a resistance differential indicative of hydrogen capacity.
A hydrogen gas storage device 10, according to one embodiment of the present invention is shown in FIG. 1. The storage device 10 comprises a storage canister 12, normally steel or aluminum bottles used for containing a hydride material for storing hydrogen, such as that disclosed in commonly assigned U.S. Pat. No. 4,396,114. The device 10 further includes an opening 14 through which the hydrogen is charged or discharged from the canister 12. The opening 14 is closed off by a hermetically sealed valve 16, controlled by a knob 15, such as are known in the prior art. Turning the knob 15 to a closed position closes off the valve 16, which should remain closed as long as the canister is not connected to another connected device (not shown) that utilizes the hydrogen stored within the canister 12, for example, a fuel cell, a nickel hydrogen electrochemical cell or a hydrogen combustion engine (not shown). The valve 16 includes a fluid outlet 18 through which the hydrogen is charged or discharged only when the fluid outlet 18 is directly connected to either a hydrogen charging or discharging connected device. In this embodiment, a fuel gauge 20 is attached to the valve 16 by a fluid communication member 22. The fuel gauge 20 may take one of several forms according to one of the several embodiments of the invention described below.
Referring now to
The face 32 of the gauge 20 is different from other pressure gauges in that it has a plurality of scales, as will be explained below with reference to the graph in FIG. 2. Several scales are necessary in order to be able to accurately gauge the amount of hydrogen capacity left within the canister 12. As is known in the hydriding field, the pressure of hydrogen gas being stored within a hydride does not correlate directly with the pressure of the hydrogen within the canister, as would be expected with a general non-hydride type storage device. Furthermore, because of the peculiar characteristics of the hydriding/dehydriding process, the temperature of the hydride and the hydrogen gas within the canister also generates variability in the amount of hydrogen gas indicated as being available for use within the canister 12.
Referring now to
The plateau pressures of the isotherms 40, 42, 44 are shown in FIG. 2. The plateau pressure of isotherm 40, indicating the pressure taken at a constant temperature of 20° C., begins at a point approximately around 50 and ends at a point approximately around 52. Isotherm 40 is described herein in an example to indicate how the amount of hydrogen being absorbed as the pressure of the hydrogen gas is increased varies with the pressure as additional pressurized hydrogen gas is introduced into canister 12. The flattening of the isotherm curve between points 50 and 52, generally recognized in the hydride field as the plateau pressure, provides the means through which this embodiment of the invention is made effective.
The plateau pressure of isotherm 40 indicates that absorption of the hydrogen gas into the hydride is most rapid during the slow pressure increase of the plateau, between points 50 and 52. As can be seen, isotherm 40 provides an increased capacity at the plateau pressure, as do the other isotherms 42 and 44. Thus, a fuel gauge that is calibrated to render it sensitive to slight variations in pressure at or around the plateau pressures would be able to provide a reasonable indication of the hydrogen capacity contained within the hydride disposed within the canister 12.
The phenomenon of hydrogen gas absorbed by the hydride over varying temperatures is a result of the isotherm of an equilibrium pressure being measured while the temperature is maintained at a constant temperature, as shown in FIG. 2. On the other hand, if the pressure of the hydrogen gas in the canister 12 is maintained at a constant value, for example, as shown in
However, the plateau pressures as shown in
A correlation is necessary between the temperature of the contents of canister 12 and the pressure that is indicated by the fuel gauge 20, which accounts for the pressure that is indicated indicative is dependent on the temperature to accurately indicate hydrogen capacity M. Thus, referring again to
Conversely, if the strip 39 shows a green color, correlating to the 25° C. isotherm the observer will note that the scale 36 is indicative that the amount of fuel present within the canister 12 is at one half capacity. Finally, if the temperature is indicated as being red by the strip 39, i.e., that the 30° C. scale is appropriate, then the observer knows to observe the scale 38, correlating to 30° C., and would know that the fuel capacity is approaching empty.
Referring now to
In another aspect of the invention, as shown in
It is a known phenomenon that hydriding/dehydriding alloys exhibit considerable expansion during the hydrogen absorption process and may expand as much as 10 to 25% in volume as the alloy absorbed from zero capacity to full capacity hydrogen. Preferably, the hydride alloy is disposed within a longitudinally extending container so as to magnify the effects of the expansion process by the shape of the container. Thus, the increase in hydrogen capacity within the specific alloy can provide greater or lesser expansion pressure depending on the amount of hydrogen that has been absorbed within that alloy.
In order for the hydrogen to be absorbed and to be indicative of the amount of hydrogen that has been absorbed within the alloy in the canister 112, there is preferably a means for communicating and providing the hydrogen in the same amount of pressure within the container 118 that is present in the remainder of the canister 112. Thus a communication means is disposed between the canister 112 and the chamber 122, such as a perforated screen (not shown) or aperture 126, as indicated in FIG. 6. The following embodiments of the invention each depend on the specific structure of the inset 114, as shown in
In one embodiment of the invention utilizing the chamber illustrated in
A single scale is shown on face 142 because the physical volumetric expansion of the contained metal hydride material depends to a much greater extent on the amount of hydrogen that is contained in the hydride material than it depends on the temperature of the hydride material. The correlation of volumetric expansion is so much more dependent on the hydrogen absorption amount that the temperature expansion effect can be effectively disregarded. However, should a more accurate reading be desired, so as to take into account the volumetric expansion of the hydride material which is contributed by an increase in temperature, a calibrated scale can also be provided to the face 142, similar to those of the faces 32, 132 shown respectively in
The diaphragm 150 (
The metal hydride material 120 is preferably identical to that of the metal hydride material in the canister 112, so that the hydrogen absorption characteristics of the hydride material contained are the same. That is, good packing of the hydride material 120 and effective distribution of the hydrogen gas introduced through the fluid communication conduit 126 will cause identical hydrogen absorption, and consequently, identical volumetric expansion of the hydride material, thus providing a reasonably accurate reading of the hydrogen capacity of the canister 112.
Alternatively, a different alloy material which is more susceptible to volumetric expansion, may be utilized within the chamber 122, so as to further magnify the effect of the hydrogen expansion. That is, metal hydride alloy material, which expands more than the general hydride material in the canister 112, will provide greater relative fluctuation in the volume of hydride material within the chamber 122, thus permitting greater precision in the reading of the scale on face 142. If two different metal hydrides are utilized, care must be taken, so that the plateau pressures of each of the hydrides can be correlated so as to accurately calibrate the scale.
Referring now to
Of course, other means of display are possible with the inventive fuel gauge. For example, the diaphragm may be coupled with an electronic pressure indicator or other type of indicator that provides the required information to the operator. For example, as shown in
The pressure sensitive plastic diaphragm 240 would have characteristics that produce a change to a different color, depending on the amount of longitudinal pressure exerted on the diaphragm 240 by the hydride material 220 contained within the chamber 222. For example, the diaphragm may be set to show a blue color when the hydrogen has been depleted from the hydride material so that no expansion of the hydride material is evident, it could show a green color when there is about ˝ capacity, when measured at or near the plateau pressure, as shown in
Referring now to
A second set of lead lines 318 is connected to a temperature sensor 322 also disposed within the canister 312, which may comprise, for example, a thermocouple or a resistance temperature device (RTD). The temperature sensor 322 also generates a signal through lead lines 318, which is also transmitted to the central processor 330 through dotted lead lines 328.
The processor 330 receives the signals transmitted by the sensors 320, 322, and through electronic manipulation using a predetermined algorithm, can compute a value for the hydrogen capacity within the canister 312. That value may be an analog or, preferably, a digital value, which may be displayed by a display 332 connected to the central processor 330. Alternatively, or in conjunction with the central processor 330, the values of the pressure and temperature sensed by sensors 320, 322 may independently corroborate that the hydrogen capacity display 332 is providing reasonable data, or the operator may utilize the data on displays 336, 338, disposed in line with the lead lines 316, 318, respectively, to independently determine the hydrogen capacity for example, by reference to a table.
Alternatively, the displays may themselves be displayed, for example, by displays 336, 338, respectively, from which values an operator either the hydrogen gas pressure within the canister 312 or alternatively, on the piezoelectric pressure sensed by a transducer 320 within the canister 312. The lead lines 316, 318 may be attached permanently to the sensor ports 314, or the lead lines may be detachable and provided with a potable microprocessor unit 330 that may be attached to the ports 314 when information about the conditions in the canister 312 is desired.
Yet another embodiment of this invention is illustrated in
External to the canister 412, the lead lines 418 are electrically connected to a device 440 for measuring electrical resistance. The device 440 may include a display 442, as shown, that indicates resistance or, alternatively, indicates the hydrogen capacity from the electric resistance signal received from the lead wires 418 and a calibrated algorithm may be accessed on a logical control circuit 444 within the device 440 so as to calculate the hydrogen capacity from the resistance signal received from within the canister 412. The lead lines 418 may also be usable with a portable stand alone resistance measuring device 440, the lead lines 418 being temporarily attachable to electrical inlet plugs (not shown) disposed within the inset portion 414, for example, similar to an electrical outlet. This feature would permit an operator to carry the measurement device 440, plug in the lead lines 418, measure the hydrogen capacity, withdraw the lead lines 418 from the inset plug and continue to monitor other devices 410.
The principle, upon which device 410 operates, depends on another characteristic of hydrides, which correlates increasing resistivity with increasing hydrogen capacity. While a direct correlation has not been definitively established, it is a smooth enough correlation to provide an accurate gauge of hydrogen capacity, after proper calibration. That is, since the increase in resistivity provides a known correlation with the hydrogen capacity contained within the hydride, knowledge of the local electrical resistance of the hydride can be translated directly to a value of hydrogen capacity. Within the context of the metal hydride alloy materials contemplated for use in this invention, it is known that the resistance may vary up to 200% between a value when no hydrogen is contained by the hydride and at or near the full saturation point of the hydride material by pressurized hydrogen.
Referring now to
The walls 426, 428 of the chamber 424 comprise an electrically insulating material that is permeable to hydrogen gas, for example TeflonŽ available from E. I. du Pont de Nemours and Company, of Wilmington, Del. The permeability of the material comprising walls 426, 428 permits the hydrogen to be absorbed and desorbed freely and equally by hydride alloy material 430 within the chamber 424. The spatial separation between the terminals 422 may be predetermined so as to provide a desired resistance between the terminals for a chamber 424 of specified size.
The chamber 424 is packed tightly with the metal hydride material 430, in powder form, to a predetermined density to provide a predetermined resistance level, which varies depending on hydrogen capacity of the hydride material 430. Preferably, the hydride material is identical in both the chamber 424 and in the remainder of canister 412, so that the hydrogen capacity of the hydride material matches throughout the device, thus providing an accurate reading of the hydrogen capacity of the hydride material within the canister 412.
During operation, a signal is transmitted from the resistance member 420 that is indicative of the resistance between the terminals 422, and is also essentially identical to the resistance of the hydride material within the canister 412. This signal is sent to a resistance measuring device 440, which analyzes the signal and utilizing calibrated algorithm accessed in the logical control circuit 444 determines the hydrogen capacity in the metal alloy hydride material in the canister 412. This embodiment provides some advantage in that the resistance measuring device 440 also absorbs hydrogen, and thus the space taken up by device 440 is not underutilized, but is utilized in the storage of the hydrogen.
Other modifications and alterations may become apparent to a person having skill in the art from an understanding of the present invention. For example, different combinations of sensors and/or colored indicators may be modified or substituted for those disclosed. Alternatively, other types of conditions may be sensed by other types of sensors not described in detail herein. For example, a weight sensor may be provided, either internally within the canister or outside, that measures the weight of the hydride material, using a tare weight for the bottle and valves, if externally measured, to provide an alternative or additional measure of hydrogen capacity. Also, Hall effect measurements of a material, such as a hydride material, are known to change the material's electromagnetic properties with increasing hydrogen capacity. It is contemplated that such a sensor may gauge the hydrogen capacity of an enclosed hydride material by inducing a magnetic field and measuring the electrical properties, such as voltage, of the material. Calibration of the material against known capacities would be required to provide accurate readings.
The above-described embodiments of the inventive hydrogen fuel gauge are to be considered as illustrative only and not limiting, the invention only being limited by the following claims.
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|International Classification||G01N25/22, G01F23/18, H01M8/04, G01N27/12, F17C11/00, G01F22/02, C01B3/00, G01F17/00, B01D53/04, F17C13/02, G01N33/20|
|Cooperative Classification||F17C11/005, G01F22/02, C01B3/0005, G01F17/00, G01F23/18, Y02E60/321, Y02E60/327|
|European Classification||G01F23/18, G01F22/02, F17C11/00D, C01B3/00D, G01F17/00|
|Oct 16, 2001||AS||Assignment|
Owner name: ERGENICS, INC., NEW JERSEY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DACOSTA, DAVID H.;GOLBEN, P. MARK;TRAGNA, DAVID C.;REEL/FRAME:012270/0758
Effective date: 20011015
|Jun 3, 2003||AS||Assignment|
Owner name: HERA USA, INC., DELAWARE
Free format text: SECURITY INTEREST;ASSIGNOR:ERGENICS INC.;REEL/FRAME:014137/0113
Effective date: 20030603
|Oct 20, 2003||AS||Assignment|
Owner name: HERA USA INC., DELAWARE
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ERGENICS, INC.;REEL/FRAME:014609/0669
Effective date: 20030925
|Mar 23, 2004||AS||Assignment|
Owner name: HERA USA INC., DELAWARE
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ERGENICS, INC.;REEL/FRAME:014453/0838
Effective date: 20030925
|Dec 30, 2008||AS||Assignment|
Owner name: ERGENICS CORP.,NEW JERSEY
Free format text: CHANGE OF NAME;ASSIGNOR:HERA USA INC.;REEL/FRAME:022034/0965
Effective date: 20070426
|Jan 25, 2011||FPAY||Fee payment|
Year of fee payment: 4
|Mar 27, 2015||REMI||Maintenance fee reminder mailed|
|Aug 14, 2015||LAPS||Lapse for failure to pay maintenance fees|
|Oct 6, 2015||FP||Expired due to failure to pay maintenance fee|
Effective date: 20150814